For efficient gas separation the membrane technology is rapidly growing day by day and it is more economical and effectual than past technologies. The main objective of this study is to synthesis polymer blend membranes (PBM) using glassy polysulfone (PSU) and rubbery polyvinyl acetate (PVAc) with the addition of methyl diethanol amine for removal of CO2 from CH4. The PBM were developed by varying the composition of PVAc ranging from 5 to 20 wt with 80 to 100 wt PSU in DMAc solvent. The amine composition was added to the blend and kept at 10 wt. The present of MDEA in the PBM had increased the CO2 permeance as compare with the based polymer membranes. However as the operating pressure increased from 2 to 10 bar, the PBM (PSU95/PVAc5) with MDEA was found to increase significantly the permeance of CO2, hence increasing the separation factor from 9.980.02 to 30.190.49. EPBM was found a very promising to be used for CO2/CH4 separation. © 2019 Chemical Society of Pakistan. All rights reserved.